CN105263860B - Ludox and silica containing composition epoxy resin - Google Patents

Abstract

A kind of Ludox, it is less than 3.0 that it contains the ratio between silica dioxide granule and silica particle diameter/average primary particle diameter for being obtained by dynamic light scattering determination, and the silica dioxide granule is as follows：Alpha-ray discharging amount is 0.005 population/cm²It is hour following, and hydroscopicity when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is below 0.5 mass %, has carried out surface modification by organic silane compound, the average primary particle diameter with 20~100nm.

Description

Ludox and silica containing composition epoxy resin

Technical field

The present invention relates to Alpha-ray discharging amount the colloidal sol of the silica dioxide granule of the nano-scale of extremely low and low moisture absorption and Composition epoxy resin and its solidfied material containing the silica dioxide granule.

Background technology

Ludox be 3~100nm or so silica dioxide granule dispersion colloidal solution in a solvent, with it is high thoroughly Bright property.Further, since silica dioxide granule has hardness high, heat resistance, so cooperation exists in resin etc. as purpose Used with the modifying agent of hardness, heat resistance in resin is assigned.

When Ludox is coupled in resin, it is contemplated that colloidal sol and resin or compatibility, the reactivity of curing agent, most feelings Scattered Ludox or the scattered Ludox in resin monomer in organic solvent are used under condition.In addition, also using surface By the situation of the SiO 2 powder of silicic acid anhydride.

For the resin used by semiconductor-sealing-purpose circuit board, semiconductor-encapsulating material, in order to reduce linear expansion coefficient And take filling silica filler.In the past, the silica filler of micron-scale has been used in these purposes.In recent years, With the miniaturization of semiconductor, the filming of circuit board, it is desirable to which the resin used in it has lower linear expansion coefficient, product Polar region has carried out the research of the silica filler filling rate in further raising resin.

When coordinating the silica filler of micron-scale with high fill-ratio in resin, there is the mobility drop of resin combination Low, treatment becomes difficult situation.Report has the surface treated silica dioxide granule by coordinating nano-scale, makes containing two Mobility lifting (patent document 1) of the resin combination of cilicon oxide filler.

On the other hand, it is higher than micron meter that the silica dioxide granule of nano-scale has hygroscopicity because its specific surface area is big The hygroscopic shortcoming of very little silica dioxide granule.During using bibulous silica filler, resin cured matter becomes easy Moisture absorption, causes deterioration, the intensity decreases of solidfied material of insulation characterisitic, the reliability reduction of device, even if therefore seeking as nanometer The also low silica dioxide granule of its hygroscopicity of size.

In addition, for encapsulant, bonding agent for semiconductor, purpose for manufacturing process's automation, it is necessary to from The position of motion detection device, it is necessary to be transparency sealing resin high.Low linear expansion system is also required that for such sealing resin Number, and require be can be with the silica dioxide granule of the scattered nano-scale of fit rate high in epoxy system resin.

Additionally, it is desirable that the radioactivity such as uranium, thorium in the silica filler that is used of foregoing electronic material purposes The content of element is few.Because the alpha ray that the radioactive element such as uranium, thorium is released can cause the maloperation of semiconductor.

In general, Ludox is roughly divided into the Ludox that is manufactured as raw material using sodium metasilicate and is made with alkyl silicate The Ludox manufactured for raw material.The Ludox manufactured as raw material using sodium metasilicate largely contains the uranium from raw material, thorium Deng radioactive element.Even if among these radioactive elements, especially sodium metasilicate is carried out ion exchange and is also difficult to be removed by thorium, Therefore it is dfficult to apply to foregoing electronic material purposes using commonly available sodium metasilicate as the Ludox of raw material.

On the other hand, using alkyl silicate as the Ludox of raw material because the purity of raw material alkyl silicate is high, so There is the low Ludox of the content of the radioactive element being readily obtained in cataloid, but low moisture absorption cannot be obtained Property silica dioxide granule, be applied to have the shortcomings that during foregoing electronic material purposes cause device performance to deteriorate.

It is commercially available to have vapor phase growth SiO 2 powder, fusion method silica as the silica filler of nano-scale Powder.These silica fillers have the advantages that hygroscopicity is low, but dispersed extreme difference in resin, cause the increasing of resin varnish It is thick etc., so being difficult to high fill-ratio.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-213514 publications

The content of the invention

Problems to be solved by the invention

Problem of the invention is to solve above-mentioned problem of the prior art, there is provided be easily filled into semiconductor-sealing-purpose wiring It is minimum and nano-scale of agent of low hygroscopicity in resin used by substrate or semiconductor-encapsulating material, containing Alpha-ray discharging amount The Ludox of silica dioxide granule, and the resin combination containing the Ludox is provided.

The scheme for solving problem

The present inventor etc. has made intensive studies, and as a result finds minimum containing Alpha-ray discharging amount and agent of low hygroscopicity receives The Ludox of the silica dioxide granule of meter ruler cun.

That is, the 1st viewpoint is Ludox, and it contains silica dioxide granule and the dioxy obtained by dynamic light scattering determination The ratio between SiClx particle diameter/average primary particle diameter is less than 3.0, and the silica dioxide granule is as follows：Alpha-ray discharging amount is 0.005 Population/cm²It is hour following, and hydroscopicity when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is 0.5 Below quality %, surface modification has been carried out by organic silane compound, the average primary particle diameter with 20~100nm；

2nd viewpoint is the Ludox recorded according to the 1st viewpoint, wherein, aforementioned organic silicon hydride compounds have epoxy radicals；

3rd viewpoint is the Ludox recorded according to the 1st viewpoint or the 2nd viewpoint, wherein, aforementioned silicas particle is in water Heated with 200~350 DEG C；

4th viewpoint is the Ludox recorded according to any one of the 1st viewpoint~the 3rd viewpoint, wherein, aforementioned silicas Grain is manufactured as initiation material so that alkali metal silicate aqueous solution is carried out into the active silicic acid that cation exchange obtains；

5th viewpoint is the Ludox recorded according to any one of the 1st viewpoint~the 3rd viewpoint, wherein, aforementioned silicas Grain is that the high-purity activity silicic acid to be obtained via following operation is manufactured as raw material, and the operation is：By alkali metal silicon Acid salt aqueous solution add in the active silicic acid that cation exchange is obtained after strong acid, further carries out cation exchange and the moon Ion exchange；

6th viewpoint is the Ludox recorded according to any one of the 1st viewpoint~the 3rd viewpoint, wherein, aforementioned silicas Grain is that the high-purity activity silicic acid to be obtained via following operation is manufactured as raw material, and the operation is：For in alkali metal The active silicic acid that cation exchange is obtained is carried out after the salt that strong acid or strong acid are added in aqueous silicate solution, sun is further carried out Ion exchange and anion exchange；

7th viewpoint is the Ludox recorded according to any one of the 1st viewpoint~the 6th viewpoint, wherein, decentralized medium is organic Solvent；

8th viewpoint is the Ludox recorded according to any one of the 1st viewpoint~the 6th viewpoint, wherein, decentralized medium is resin Monomer；

9th viewpoint is the Ludox recorded according to the 8th viewpoint, wherein, aforementioned resin monomer is epoxy monomer；

10th viewpoint is SiO 2 powder, and it is removed from the Ludox of any one of the 1st viewpoint~the 9th viewpoint record Go obtained from decentralized medium；

11st viewpoint is silica containing composition epoxy resin, and it contains：Any one of 1st viewpoint~the 9th viewpoint SiO 2 powder and epoxy monomer and epoxy hardener that the Ludox of record or the 10th viewpoint are recorded；

12nd viewpoint is silica containing composition epoxy resin, and it is from the silica containing of the 11st viewpoint record Obtained from eliminating organic solvent in composition epoxy resin；

13rd viewpoint is the silica containing composition epoxy resin recorded according to the 11st viewpoint or the 12nd viewpoint, its In, silica containing ratio is 10~90 mass %；

14th viewpoint is silica containing epoxy resin cured product, and it is to make any one of the 11st viewpoint~the 13rd viewpoint Obtained from the silica containing epoxy resin composition recorded.

The effect of invention

Ludox of the invention is the silica of and nano-scale of agent of low hygroscopicity minimum containing Alpha-ray discharging amount The Ludox of grain, is easily coupled in the resin used by semiconductor-sealing-purpose circuit board, semiconductor-encapsulating material, is capable of achieving low Linear expansion coefficient.

Specific embodiment

Hereinafter, it is described in detail for Ludox of the invention.Ludox of the invention be containing silica dioxide granule, It is described and the ratio between the silica particle diameter/average primary particle diameter obtained by dynamic light scattering determination is less than 3.0 Ludox Silica dioxide granule is as follows：Alpha-ray discharging amount is 0.005 population/cm²Below hour, and in 23 DEG C, relative humidity Hydroscopicity when being placed 48 hours in the environment of 50RH% is below 0.5 mass %, and surface has been carried out by organic silane compound Modification, the average primary particle diameter with 20~100nm.

The Alpha-ray discharging amount of silica dioxide granule can be used 2 π air-flow counting mode low-levels alpha rays to determine device, example LACS-4000M such as Sumitomo Chemical Co's manufacture is measured to the powder by dry silica dioxide granule.

In the present invention, moisture absorption of the silica dioxide granule when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% Rate will can be placed 48 hours by the powder of dry silica dioxide granule by determining in the environment of relative humidity 50RH% When weight change and calculate.Specifically, Silica hydrogel that Ludox obtains will be dried in mortar with 80 DEG C of vacuum driers After crushing, further silica dried powder is obtained in 180 DEG C of dryings 3 hours.The dried powder is collected into 0.2g In measuring cup, gravimetry.The measuring cup stands 48 hours in the state of uncapping under 23 DEG C, the atmosphere of relative humidity 50RH% Afterwards, closing lid and again gravimetry.Then, hydroscopicity is calculated by following formula.

Hydroscopicity (%)=(increasing the example weight of weight/collection) × 100

The hydroscopicity of the silica dioxide granule contained by Ludox of the invention is below 0.5 mass %, preferably 0.3 matter Amount below %, more preferably below 0.2 mass %.

The average primary particle diameter of the silica dioxide granule contained by Ludox of the invention can be used and dry the silica The specific surface area based on nitrogen adsorption method of the SiO 2 powder that particle is obtained, calculated by following conversion formula.

Conversion formula：Average primary particle diameter (nm)=2720/ is based on the specific surface area (m of nitrogen adsorption method²/g)

The primary particle size of the silica dioxide granule contained by Ludox of the invention be 20~100nm, preferably 30~80nm, More preferably 40~70nm.

In the present invention, the silica particle diameter obtained by dynamic light scattering determination can be measured：For Ludox, make With with its decentralized medium identical solvent, 10~100 times are diluted to based on volume reference, use dynamic light scattering method particle diameter Device, the Zetasizer Nano of such as Malvern Instruments manufactures is determined to be surveyed in the form of average particle size of the dispersion It is fixed.

In addition, be not particularly limited for the manufacture method of Ludox of the invention, with preferably 200~350 such as in water DEG C, more preferably 230~300 DEG C heated.The heating can be implemented using pressure vessel (autoclave).

In addition, Ludox of the invention is preferably to carry out the activity that dealkalize metal is obtained with by alkali metal silicate aqueous solution Silicic acid is manufactured as initiation material.As alkali metal silicate aqueous solution, sodium silicate aqueous solution, potassium silicate water can be included Solution etc..The dealkalize metal of alkali metal silicate aqueous solution is suitably for using the ion-exchange of cationic ion-exchange resin.Additionally, Can also be using as being neutralized with acid and active silicic acid obtained from cleaning the method for removing generated alkali metal salt is used as initial former Material is used.

In addition, Ludox of the invention is more preferably using the high-purity activity silicic acid obtained via following operation as raw material And manufacture, the operation is：Strong acid is added in alkali metal silicate aqueous solution is carried out into the active silicic acid that dealkalize metal is obtained Afterwards, cation exchange is carried out.The dealkalize metal of alkali metal silicate aqueous solution be suitably for use cationic ion-exchange resin from Sub- exchange process.As strong acid used, hydrochloric acid, sulfuric acid, nitric acid etc. can be included.

Ludox of the invention can be manufactured by following method, but be not limited to the method.As used by initiation material Alkali metal silicate aqueous solution can for example use commercially available JIS3 sodium silicate aqueous solutions.Sodium silicate aqueous solution is diluted with water Into the mass % of silica concentration about 1~5, so as to modulate dilute sodium silicate aqueous solution.By its filled with hydrogen type strong acid sun from Lead to liquid in the post of sub-exchange resin, so as to obtain the active silicic acid aqueous solution.In the active silicic acid aqueous solution of gained add hydrochloric acid, Sulfuric acid or nitric acid, the pH of the active silicic acid aqueous solution is adjusted to 0~2, and holding 1~24 is small at the temperature below room temperature~60 DEG C When.Then lead to liquid in the post filled with hydro-strong acidic cation exchange resin, so filled with oh type alkalescence it is cloudy from Lead to liquid in the post of sub-exchange resin, obtain the active silicic acid aqueous solution of high-purity.It is water-soluble in the active silicic acid of the high-purity of gained The aqueous solution of NaOH or potassium hydroxide is added in liquid, pH is adjusted to 7~9, so as to obtain stabilized activated silica acid solution. It is for the stabilized active silicic acid aqueous solution, it is preferred that silica concentration is for about 1~5 mass %, sodium atom or potassium is former Sublist is shown as M, makes SiO₂/M₂O mol ratios are 50~250.70~150 DEG C are heated to by by the stabilized active silicic acid, from And obtain the high-purity water dispersion Ludox that average primary particle diameter is 10~30nm.The high-purity water dispersion Ludox of gained enters one Step is heated at a high temperature of 200~350 DEG C, so that silica dioxide granule becomes fine and close, can obtain hygroscopicity low Silica dioxide granule.The method that heating under high temperature is implemented preferably in water.

Silica dioxide granule contained by Ludox of the invention has carried out surface modification by organic silane compound.As table Face modification organic silane compound used, can include silazane, siloxanes or alkoxy silane and its partial hydrolystate or The oligomer of its 2 aggressiveness~5 aggressiveness.

As silazane, for example, can include HMDS, hexaethyl disilazine.

As siloxanes, for example, can include HMDO, 1,3- dibutyl tetramethyl disiloxane, 1,3- bis- Phenyl tetramethyl disiloxane, 1,3- divinyl tetramethyl disiloxanes, hexaethyldisiloxane, 3- glycidoxypropyl groups Pentamethyl disiloxane.

As alkoxy silane, for example, can include trimethylmethoxysilane, trimethylethoxysilane, trimethyl third TMOS, pheiiyldimetliyl methoxy silane, chloropropyl dimethyl methoxy silane, dimethyldimethoxysil,ne, methyl Trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, ethyl trimethoxy Silane, dimethyldiethoxysilane, propyl-triethoxysilicane, n-butyltrimethoxysilane, n-hexyl trimethoxy silicon Alkane, n-octytriethoxysilane, n-octyl methyldiethoxysilane, n-octadecane base trimethoxy silane, phenyl front three TMOS, phenyl methyl dimethoxysilane, phenethyl trimethoxy silane, dodecyltrimethoxysilane, positive 18 Alkyl triethoxysilane, phenyltrimethoxysila,e, dimethoxydiphenylsilane, vinyltrimethoxy silane, ethene Ethyl triethoxy silicane alkane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silicon Alkane, γ-acryloxypropyl trimethoxy silane, γ-(methacryloxypropyl) methyl dimethoxysilane, γ- Methacryloyloxypropyl methyl diethoxy silane, γ-methacryloxypropyl, β-(3,4- Epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl group first Base diethoxy silane, γ-glycidoxypropyl group triethoxysilane, N- β (aminoethyl)-γ-(aminopropyl) methyl dimethoxy TMOS, N- β (aminoethyl)-γ-(aminopropyl) trimethoxy silane, N- β (aminoethyl)-γ-(aminopropyl) triethoxy Silane, γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, N- phenyl-γ-aminopropyl trimethoxy silicon Alkane, γ-mercaptopropyl trimethoxysilane, 3- NCOs propyl-triethoxysilicane, trifluoro propyl trimethoxy silane, ten Seven alkyl trifluoro propyl trimethoxy silanes, positive decyl trimethoxy silane, dimethoxy diethoxy silane, double (three ethoxies Base silicyl) ethane, six ethyoxyl disiloxane.

As the organic silane compound used by surface modification, the preferably organic silane compound with epoxy radicals.As Organic silane compound with epoxy radicals, can include β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-epoxy Propoxypropyl trimethoxy silane, γ-glycidoxypropyl diethoxy silane, γ-glycidoxypropyl group three Ethoxysilane etc..

For the surface modification of silica dioxide granule, it is preferred that relative to the surface area of silica dioxide granule 1nm²Amount use with the molecule of organic silane compound for 0.1~5 carries out surface modification.The surface of silica dioxide granule Modify and added preferably in water dispersible silicone colloidal sol or organic solvent dispersion Ludox the organic silane compound of ormal weight and stirring Mixing down to heat 0.5~24 hour with 5~100 DEG C is carried out.In order to promote using the surface modification of organic silane compound, Can also the catalyst such as acid, alkali be added in right amount to implement.

The decentralized medium of Ludox of the invention is water, organic solvent or resin monomer.

For the organic solvent of the decentralized medium as Ludox of the invention, alcohol, ketone, ether, ester, hydrocarbon etc. can be included. In addition, organic solvent used can be a kind, it is also possible to which two or more is used in mixed way.Organic solvent dispersion Ludox can be used The known methods such as the water dispersible silicone colloidal sol way of distillation carry out solvent displacement to obtain.

As alcohol, methyl alcohol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, 1- can be included Amylalcohol, 1- hexanols, 1- octanols, 2- ethyl -1- hexanols, allyl alcohol, benzylalcohol, cyclohexanol, 1,2- ethylene glycol, 1,2- propane diols, 2- Methyl cellosolve, cellosolvo, 2- allyloxyethanols, 2- (methoxy ethoxy) ethanol, 1- methoxy-2-propanols, two Propylene glycol monomethyl ether, DAA, ethyl carbitol, butyl carbitol etc..

As ketone, can include acetone, MEK, 2 pentanone, propione, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK), 2-HEPTANONE, 4- heptanone, DIBK, cyclohexanone etc..

As ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, dioxs, tetrahydrofuran, 1,2- diethyls can be included Epoxide ethane etc..

As ester, can include Ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, Butyl acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, Gamma-butyrolacton, methyl methacrylate, isobutyl acrylate, cyclohexyl acrylate, acrylic acid 2- ethoxy ethyl esters, acrylic acid Trifluoro ethyl ester, GMA etc..

As hydrocarbon, n-hexane, hexamethylene, benzene,toluene,xylene, solvent naphtha (solvent can be included Naphtha), halogenated hydrocarbons such as styrene or dichloromethane, trichloro ethylene etc..

For the resin monomer of the decentralized medium as Ludox of the invention, can include with ethylenic unsaturated bond Resin monomer, the resin monomer with epoxide ring, the resin monomer with oxetanes ring etc..Resin monomer disperses Ludox Resin monomer can be replaced into by by the known method such as water dispersible silicone colloidal sol or the organic solvent dispersion Ludox way of distillation To obtain.

As the resin monomer with ethylenic unsaturated bond, for example, can include acrylic acid, methacrylic acid, itaconic acid, The unsaturated carboxylic acid compounds such as crotonic acid, maleic acid, phthalic acid.

It is esterified in addition, can include and derive the unsaturated carboxylic acid for obtaining by foregoing unsaturated carboxylic acid compounds and alcoholic compound Compound.For example, acrylate compounds, methacrylate compound, itaconate compound, crotonates compound, horse Come ester compound, phthalic acid ester compounds.Unsaturated carboxylic acid is generated as being reacted with foregoing unsaturated carboxylic acid compounds The alcoholic compound of ester, is not particularly limited, and can include ethylene glycol, triethylene glycol, TEG, three (2- hydroxyethyls) trimerizations Isocyanic acid, triethanolamine, pentaerythrite etc. for example have 2~6 polyol compounds of hydroxyl.

In addition, can include that the unsaturated carboxylic acid acid amides for obtaining is derived by foregoing unsaturated carboxylic acid compounds and amines Compound.For example, acrylamide compound, methacrylamide compounds, clothing furoyl amines, crotonamide compound, Maleic amide compound, phenyl-diformyl amines etc..As amine compound, it is not particularly limited, second two can be included Amine, DACH, diaminonaphthalene, 1,4- double (aminomethyl) hexamethylene, 3,3 ', 4,4 '-tetra-amino-biphenyl, three (2- amino Ethyl) amine etc. for example has the polyhydric amine compounds of 2~6 primary amino radicals or secondary amino group.

As the concrete example of the resin monomer with ethylenic unsaturated bond, ethylene glycol two (methyl) acrylic acid can be included Ester, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylic acid Ester, nine ethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylic acid Ester, four propane diols two (methyl) acrylate, nine propane diols two (methyl) acrylate, polypropylene glycol two (methyl) acrylic acid Ester, 2,2- double (4- ((methyl) acryloxy diethoxy) phenyl) propane, 3- phenoxy group -2- propionos acrylate, 1, 6- double (3- acryloxy -2- hydroxypropyls) hexyl ether, trimethylolpropane tris (methyl) acrylate, glycerine three (methyl) third Olefin(e) acid ester, three (2- hydroxyethyls) isocyanuric acid ester (methyl) acrylate, pentaerythrite three (methyl) acrylate, season penta Tetrol four (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two Pentaerythrite six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylic acid Ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) 2-EHA, 2- norbornane ylmethyl methacrylic acids Ester, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, (methyl) acrylic acid 2- hydroxy methacrylates, acrylic acid 2,2- dimethyl butyrates Ester, (methyl) acrylic acid 2- hydroxybutyls, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) tert-butyl acrylate, (methyl) the just own ester of acrylic acid, (methyl) acrylic acid n-pentyl ester, (methyl) acrylic acid N-octyl, (methyl) acrylic acid 2- methoxy acrylates, acrylic acid 2- methoxymethoxies ethyl ester, (methyl) acrylic acid 3- pentyl esters, 3- methyl -2- norbornanes methyl methacrylate, (methyl) acrylic acid 3- methoxybutyls, (methyl) acrylic acid 4- hydroxyls Base butyl ester, acrylic acid 4- methyl-2-propyls pentyl ester, 5- ENB -2- methyl methacrylates, (methyl) acrylic acid are different Propyl ester, (methyl) acrylic acid n-octadecane base ester, the positive nonyl ester of (methyl) acrylic acid, (methyl) sec-butyl acrylate, (methyl) third Olefin(e) acid tert-pentyl ester, Alpha-hydroxy EMA, Alpha-hydroxy butyl methacrylate, Alpha-hydroxy methyl methacrylate, (first Base) acrylic acid, the positive stearyl ester of acrylic acid, Isooctyl acrylate monomer, the different nonyl ester of acrylic acid, (methyl) acrylic acid norborneol ester, (first Base) ethyl acrylate, ethyl carbitol acrylate, (methyl) ethoxyethyl acrylate, (methyl) ethioxy second Epoxide ethyl ester, ethoxydiglycol acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylate base methyl esters, third Olefin(e) acid ring pentyl ester, acrylic acid bicyclopentadiene epoxide ethyl ester, acrylic acid cetyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) Acrylate, phthalic acid hydrogen (methyl) acryloyloxyethyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid Methyl esters, (methyl) methoxyethyl acrylate, (methyl) methoxyethyl ethoxy ethyl ester, methoxy poly (ethylene glycol) (methyl) Acrylate, (methyl) lauryl acrylate, 1,3 butylene glycol two (methyl) acrylate, 1,4- butanediols two (methyl) propylene Acid esters, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, glycerine two (methyl) acrylate, dicyclopentadienyl two (methyl) acrylate, tristane diformazan Alcohol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, NPGA neopentyl glycol adipate two (methyl) propylene Acid esters, neopentyl glycol two (methyl) acrylate, neopentyl glycol 3-hydroxypivalic acid ester diacrylate, ethoxylation trihydroxy methyl Propane three (methyl) acrylate, glycerine propoxyl group three (methyl) acrylate, trimethylolpropane polyethoxy three (methyl) Acrylate, propionic acid are modified dipentaerythritol three (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, third Modified dipentaerythritol four (methyl) acrylate of acid, pentaerythritol propoxylate four (methyl) acrylate, propionic acid modified two Pentaerythrite five (methyl) acrylate, GMA, N, N- DMAAs, N, N- diethyl third Acrylamide, vinyl benzene, divinylbenzene, vinyltoluene, styrene, AMS, p-methylstyrene etc..Need Illustrate, wherein for example ethylene glycol two (methyl) acrylate means glycol diacrylate and ethylene glycol dimethyl propylene Acid esters.

In addition, used as the foregoing resin monomer with ethylenic unsaturated bond, can also include can be by polyisocyanates Urethanes obtained from the reaction of compound and unsaturated carboxylic acid hydroxy alkyl ester compounds, can be by polynary epoxidation Compound and two allyls such as compound, dially phthalate obtained from the reaction of unsaturated carboxylic acid hydroxy alkyl ester compounds The divinyl compounds such as ester compounds, divinyl phthalic acid ester.

As the resin monomer with epoxide ring, it is possible to use with 1~6 compound of epoxide ring.With 1~6 The polymerizable compound of epoxide ring can be included for example can be by diol compound, three alcoholic compounds, dicarboxylic acid compound, three The glycidyl compounds such as the compound with more than 2 hydroxyls or carboxyl such as carboxylic acid compound and epichlorohydrin come it is manufacturing, Compound with more than 2 glycidol ether structures or glycidol ester structure.

As the concrete example of the resin monomer with epoxide ring, BDDE, 1,2- can be included Epoxy radicals -4- (epoxy ethyl) hexamethylene, T 55, diethylene glycol diglycidyl glycerin ether, 2,6- bis- shrink sweet Oil base phenyl glycidyl ether, 1,1,3- tri- [to (2,3- glycidoxies) phenyl] propane, 1,2- cyclohexane cyclohexanedimethanodibasics two contract Water glyceride, 4,4 '-di-2-ethylhexylphosphine oxide (N, N- diglycidylaniline), 3,4- epoxycyclohexyl-methyl -3,4- epoxy hexamethylenes Alkane formic acid esters, trimethylolethane trimethacrylate glycidol ether, triglycidyl group para-aminophenol, four glycidyl group isophthalic two The double aminomethyl cyclohexanes of amine, four glycidyl group diaminodiphenyl-methane, four glycidyl group -1,3-, bisphenol-A two shrink sweet Oily ether, bisphenol-S diglycidyl ether, the glycidol ether resorcinolformaldehyde resin of pentaerythrite four, phthalic acid two contract Water glyceride, neopentylglycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bis-phenol Hexafluoro acetone diglycidyl ether, pentaerythrite diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, three (2,3- epoxies third Base) isocyanuric acid ester, double (2,3- the glycidyl) -1,3,5- triazines -2,4,6- of 1- { 2,3- bis- (propionyloxy) } -3,5- Double { 2,3- bis- (propionyloxy) } -5- (2,3- the glycidyl) -1,3,5- triazines -2,4,6- of (1H, 3H, 5H)-triketone, 1,3- (1H, 3H, 5H)-triketone, monoallyl diglycidyl isocyanuric acid ester, the poly- diglycidyl ether of two glycerine, Ji Wusi Alcohol polyglycidyl ether, 1,4- double (2,3- glycidoxies perfluoroisopropyl) hexamethylene, d-sorbite polyglycidyl ether, three Hydroxymethyl-propane polyglycidyl ether, resorcinolformaldehyde resin, 1,6 hexanediol diglycidylether, polyethylene glycol two Glycidol ether, phenyl glycidyl ether, to tert-butyl-phenyl glycidol ether, adipic acid diglycidyl ether, O-phthalic Sour diglycidyl ether, dibromo phenyl glycidol ether, 1,2,7,8- diepoxyoctanes, 1,6- dihydroxymethyls perflexane two contract Double (the 4- glycidoxies phenyl) third of water glycerin ether, 4,4 '-bis- (2,3- glycidoxies perfluoroisopropyl) diphenyl ether, 2,2- Alkane, 3,4- epoxycyclohexyl-methyls -3 ', 4 ' -7-oxa-bicyclo[4.1.0 formic acid esters, 3,4- epoxycyclohexyls oxirane, 2- (3,4- rings Oxygen cyclohexyl) -3 ', 4 '-epoxy radicals -1,3- diox -5- volutions hexane, 1,2- ethylenes epoxide-bis- (3,4- epoxy hexamethylenes Methylmethane), 4 ', 5 '-epoxy radicals -2 '-methylcyclohexylmethyl -4,5- epoxy radicals -2- cyclohexanecarboxylic acids ester, ethylene glycol - Double (3,4- 7-oxa-bicyclo[4.1.0s formic acid esters), double (3,4- epoxycyclohexyl-methyls) adipate esters, double (2,3- epoxycyclopentyls) ethers Deng.

As the resin monomer with oxetanes ring, it is possible to use with 1~6 chemical combination of oxetanes ring Thing.For example, 3- ethyl -3- hydroxymethyl-oxetanes, 3- ethyls -3- (phenoxymethyl) oxetanes, 3 can be included, 3- diethyl oxetanes and the double (((3- ethyls -3- of 3- ethyls -3- (2- Ethylhexoxymethyls) oxetanes, 1,4- Oxetanyl) methoxyl group) methyl) benzene, two ((3- ethyl -3- oxetanyls) methyl) ethers and pentaerythrite four ((3- ethyl -3- oxetanyls) methyl) ether etc..

Ludox of the invention can be obtained with the solation that silica concentration is 1~70 mass %.

The present invention is still by SiO 2 powder obtained from Ludox of the invention drying below 250 DEG C.Dry temperature When degree is more than 250 DEG C, decomposed as the organic silane compound of coating material sometimes.

The present invention is still by Ludox of the invention or SiO 2 powder of the invention and epoxy monomer and epoxy The silica containing composition epoxy resin that curing agent is obtained by mixing.

As epoxy monomer used when obtaining silica containing composition epoxy resin of the invention, can make With the foregoing resin monomer with epoxide ring.

As epoxy hardener, phenolic resin, amine, polyamide, imidazoles, polythiol, acid anhydrides, sun can be included Cation polymerization initiator etc..

As phenolic resin, for example, can include phenol resol resins, cresol novolac resin etc..

As amine, for example, can include piperidines, N, N- lupetazins, triethylenediamine, 2,4,6- tri- (dimethylamino first Base) phenol, benzyl dimethylamine, 2- (dimethylamino methyl) phenol, Diethylenetriamine, three second tetramines, tetren, lignocaine third Amine, N- aminoethyl piperazines, two (1- methyl-2-aminos cyclohexyl) methane,Alkene diamines, IPD, the ring of diaminourea two Hexyl methane, 1,3- diaminomethyls hexamethylene, benzene dimethylamine, m-phenylene diamine (MPD), diaminodiphenyl-methane, DADPS Deng.Diethylenetriamine, three second tetramines, tetren, diethylaminopropylamine, the N- ammonia second of liquid can be preferably used among them Base piperazine, two (1- methyl-2-aminos cyclohexyl) methane,Alkene diamines, IPD, diamino-dicyclohexyl methane Deng.

It is to be condensed by dimeric dibasic acid and polyamines and generate, there is in molecule gathering for primary amine and secondary amine as polyamide Amide amine.

As imidazoles, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1- cyanoethyl -2- undecyl miaows can be included Azoles trimellitic acid salt, epoxy ifyzidazole adduct etc..

Polythiol is, for example, polythiol, the end presence in polyglycol chain that there is sulfydryl in the end of polypropylene glycol chain The polythiol of the polythiol of sulfydryl, preferably liquid.

As acid anhydrides, there is the acid anhydrides of the compound of multiple carboxyls in a preferably molecule.As these acid anhydrides, can include The double trimellitates of phthalate anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, ethylene glycol, glycerine three are inclined Benzenetricarboxylic acid ester, maleic anhydride, tetrahydrochysene phthalate anhydride, methyl tetrahydrochysene phthalate anhydride, endo-methylene group tetrahydrochysene phthalate anhydride, first Base endo-methylene group tetrahydrochysene phthalate anhydride, methyl butene base tetrahydrochysene phthalate anhydride, dodecenyl succinic anhydride, hexahydrobenzene diformazan Acid anhydrides, methyl hexahydrophthalic acid anhydride, succinyl oxide, methylcyclohexene dicarboxylic acid anhydride, chlorendic anhydride etc..

As cationic polymerization initiators, it is possible to use release the initiation of the material for triggering cationic polymerization because of light or heat Agent.

As light cationic polymerization initiator, for example, aromatic diazonium salt, aromatic halonium salts, aromatic matte can be included The salts such as salt；Organic gold such as iron-aromatic hydrocarbons complex, titanocenes complex, aryl-silane alcohol-aluminium complex Category ligand compound species；P-Nitrobenzyl, sulfonic acid, phosphate, sulfocarbolate, diazonium quinone, N- hydroxy imide sulfonate Deng.As the commercially available product of light cationic polymerization initiator, for example, " ADEKA OPTOMER SP150 ", " ADEKA can be included OPTOMER SP170 " etc. " ADEKA OPTOMER " series (ADEKA CORPORATION systems)；UVACURE1591 (UCB. S.A. (BE) Bruxelles Belgium System)；CD-1010, CD-1011, CD-1012 (SARTOMER company systems)；(the Ciba-Geigy of IRGACURE (registration mark) 264 Japan Limited systems)；CIT-1682 (NIPPON SODA CO., LTD. system) etc..

As hot cationic polymerization, the open loop that ring-opening polymerization group is activated, lured into by heating can be used Any hot cationic polymerization, the various salts such as quaternary ammonium salt, phosphonium salts, sulfonium salt can be exemplified.

As foregoing quaternary ammonium salt, for example, TBuA tetrafluoroborate, TBuA hexafluorophosphate, four can be included Butyl ammonium bisulphate salt, tetraethyl ammonium tetrafluoroborate, tetraethyl ammonium tosilate, N, N- Dimethyl-NBenzyl aniline Hexafluoro antimonate, N, N- Dimethyl-NBenzyl aniline tetrafluoroborate, N, N- Dimethyl-NBenzyl pyridines hexafluoro antimonate, N, N- diethyl-N- benzyls fluoroform sulphonate, N, N- dimethyl-N -s (4- methoxy-benzyls) pyridine hexafluoro antimonate, N, N- bis- Ethyl-N- (4- methoxy-benzyls) toluene amido hexafluoro antimonate etc..

As Qian Shu phosphonium salts, for example, Yi base triphenyl phosphoniums hexafluoro antimonate, 4-butyl-phosphonium hexafluoro antimonate can be included Deng.

As foregoing sulfonium salt, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoro antimonate, triphen can be included Base sulfonium hexafluoro arsenate, three (4- methoxyphenyls) sulfonium hexafluoro arsenates, diphenyl (4- Phenylsulfanylphenyls) sulfonium hexafluoro arsenate Deng.

As the commercially available product of foregoing hot cationic polymerization, for example, ADEKA OPTON (registration mark) can be included CP-66, ADEKA OPTON (registration mark) CP-77 (ADEKA CORPORATION systems)；サ Application エ イ De (registration mark) SI- 60L, サ Application エ イ De (registration mark) SI-80L, サ Application エ イ De (registration mark) SI-100L (three new chemical industry strain formula meetings Society's system)；CI series (NIPPON SODA CO., LTD. system) etc..

In addition, when obtaining silica containing composition epoxy resin of the invention, suitably can be promoted using solidification in the lump Enter agent.As curing accelerator, the organic phosphorus compounds such as triphenylphosphine, tributylphosphine can be included；The phenyl-bromide Phosphonium of second base three, Jia base triphenyl phosphonium diethyl phosphate Deng quaternary alkylphosphonium salts；Carbon -7- the alkene of 1,8- diazabicyclos (5,4,0) 11,1,8- diazas are double The quaternary ammonium salts such as salt, zinc octoate, the TBAB of the carbon -7- alkene of ring (5,4,0) 11 and octanoic acid.These curing accelerators can be with Contained with the ratio of 0.001~0.1 mass parts relative to the mass parts of epoxy hardener 1.

When obtaining silica containing composition epoxy resin of the invention, the method for mixing is not particularly limited, Blender or kneading machine are preferably used so that Ludox or SiO 2 powder are equably mixed with epoxy resin and epoxy hardener Close, for example, it is preferable to be carried out under being sufficiently stirred for from revolution type mixer.

The viscosity of silica containing composition epoxy resin is high, will not carry out rapidly it is mixed uniformly in the case of, can lead to The degree do not aggravated with curing reaction is crossed to be heated and viscosity reduction is carried out lifting operation.

In addition, in the case of including organic solvent in aforementioned epoxy curing agent, the silica containing epoxy resin of gained Organic solvent is included in composition, is preferably depressurized or is heated so as to remove organic solvent by said composition.

Silica containing composition epoxy resin of the invention can be solidified using heat or light and be obtained containing dioxy The epoxy resin cured product of SiClx.

The heat curing temperature of silica containing epoxy composite of the invention is 80~200 DEG C or so, heat cure with 1~ Implement within 12 hours or so.Heating can use the devices such as baking oven.

As the active energy beam that the photocuring of silica containing epoxy composite of the invention is used, wavelength model Enclose for 150~500nm, be preferably 300~400nm, energy is preferably 10~3000mJ/cm².It is preferable as the light source for using Be low pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, carbon arc lamp, ultraviolet fluorescent lamp, chemical lamp, xenon lamp, zirconium lamp etc..

Embodiment

[embodiment 1]

Operation (a)：As the water-soluble alkali metal silicates of raw material, prepare the sodium silicate aqueous solution of No. JIS3.The silicic acid The main component than water of sodium water solution is SiO₂28.8 mass %, Na₂O9.47 mass %.By above-mentioned sodium silicate aqueous solution 52.5kg is dissolved in pure water 367.5kg, so as to be prepared for SiO₂Concentration is the sodium silicate aqueous solution 420kg of 3.6 mass %.Then, By 25 DEG C of above-mentioned sodium silicate aqueous solution filled with hydro-strong acidic cation exchange resin Amberlite (registration mark) After carrying out logical liquid as 3 with the space velocity of every 1 hour in the post of IR-120B, by the SiO of gained₂Concentration be 3.6 mass %, PH is that the activated silica aqueous acid 357kg of 25 DEG C of 2.93 is recovered in container.

Operation (b)：As the strong acid for being used, prepare the sulfuric acid (Northeast chemistry strain formula of the special grade chemical of commercially available product Commercial firm's system) with pure water dilute obtained from 10 mass % sulfuric acid.In the activated silica aqueous acid obtained by operation (a) The sulfuric acid 8.9kg of above-mentioned 10 mass % is added in 357kg, makes pH to keep 48 hours at 1.54,20 DEG C so as to terminate operation (b)。

Operation (c)：The activated silica aqueous acid 365.9kg for being added with sulfuric acid that will be obtained by above-mentioned operation (b) is being filled out Filled with 20 liters about 25 DEG C of hydro-strong acidic cation exchange resin Amberlite (registration mark) IR-120B of posts with every 1 The space velocity of hour carries out logical liquid for 5.The total amount of liquid of gained is then handed over filled with 50 liters of oh type strong alkalinity anions In the post of change Resin A mberlite (registration mark) IRA-410 about 25 DEG C logical liquid is carried out with the space velocity of every 1 hour as 2. Then, the total amount of liquid of gained is different filled with 10 liters of hydro-strong acidic cation exchange resins from previously used Logical liquid is carried out with the space velocity of every 1 hour as 10 in the post of about 25 DEG C of Amberlite (registration mark) IR-120B, by institute The total amount 362.3kg for obtaining is recovered in container.This by the activated silica aqueous acid of ion exchange SiO₂Concentration is 3.5 matter Amount %, pH are 4.38.

Operation (d)：By the way that the NaOH (Kanto Kagaku K. K.'s system) of commercially available special grade chemical is dissolved in into pure water and The active silicic acid by ion exchange that the mass % aqueous solution 2.1kg of NaOH 10 additions for obtaining are obtained by operation (c) Aqueous solution 362.3kg, so as to obtain stabilized activated silica aqueous acid.The SiO of the aqueous solution₂Concentration be 3.5 mass %, SiO₂/Na₂O mol ratios are that 80, pH is 8.20.

Operation (e)：The stabilisation obtained by operation (d) is put into the stainless steel autoclave reactor of 3 liters of internal volume Activated silica aqueous acid 2.8kg, 5 hours hydro-thermal process are carried out at 130 DEG C.The hydro-thermal process carries out 5 times and obtains hydro-thermal Treatment reactant 14kg.The hydrothermal process thing is, SiO₂Concentration is that 3.5 mass %, pH are that 10.3, average primary particle diameter is 13nm, the silica particle diameter obtained by dynamic light scattering determination are the alkaline silica sol of 22nm.

Operation (f)：For the alkaline silica sol obtained by operation (e), concentrated using ultra-filtration membrane device, obtained SiO₂ Concentration is the alkaline silica sol 1.6kg that 31.0 mass %, pH are 9.27.

Operation (g)：The alkaline silica sol 1.6kg that will be obtained by operation (f) is filled with hydrogen type strong acid cation exchange In the post of about 25 DEG C of Resin A mberlite (registration mark) IR-120B logical liquid is carried out with the space velocity of every 1 hour as 5.Connect , the NaOH of the special grade chemical of commercially available product is dissolved in the mass % aqueous solution of NaOH 10 obtained from pure water by addition 16.3g, alkaline silica sol is adjusted to SiO₂Concentration is that 30.0 mass %, pH are 8.20, SiO₂/Na₂O mol ratios are 400.

Operation (h)：In the SUS autoclave reactors of 3 liters of internal volume, input is through operation (g) by SiO₂/Na₂O moles Than adjusting to 400 alkaline silica sol 1.5kg, 30 minutes 2 hours hydro-thermal process are carried out at 245 DEG C.The Ludox of gained is as follows： PH is 10.2, average primary particle diameter for 45nm, the silica particle diameter obtained by dynamic light scattering determination are 74nm.

Operation (i)：The alkaline silica sol 1.5kg that will be obtained by operation (h) is filled with hydrogen type strong acid cation exchange Logical liquid is carried out with the space velocity of every 1 hour as 10 in the post of about 25 DEG C of Resin A mberlite (registration mark) IR-120B, So as to obtain SiO₂Concentration is the acidic silicasol that 30.0 mass %, pH are 3.50.

Operation (j)：The acidic silicasol 1200g that will be obtained by operation (i) is dosed in 2 liters of removable flask, on one side Stirring is while addition methyl alcohol 200g and Tri-n-Propylamine 1.0g.Then, solvent is carried out when methanol gas are supplied in Ludox to put Change, so as to obtain SiO₂The methyl alcohol dispersion Ludox 1800g that concentration is 20 mass %, moisture is 1.2 mass %.

Operation (k)：The methyl alcohol dispersion Ludox 1000g that will be obtained by operation (j) is dosed to 2 liters of eggplant type flask, on one side It is stirred with magnetic stirring apparatus, while addition phenyltrimethoxysila,e 12.1g, is heated to 60 DEG C and is kept for 3 hours.Addition Surface area 1nm of the phenyltrimethoxysila,e relative to the silica dioxide granule in the colloidal sol²It is equivalent to 3.0.Then, Eggplant type flask is installed in Rotary Evaporators, supply MEK under 80 DEG C of bath temperature, the decompression of 500~350 supports while Distilled, so as to obtain MEK dispersion Ludox.The colloidal sol of gained is as follows：SiO₂Concentration is 30.5 mass %, moisture is The silica particle diameter that 0.03 mass %, methyl alcohol is 0.5 mass %, obtained by dynamic light scattering determination is 74nm, by dynamic The ratio between silica particle diameter/average primary particle diameter that light scattering determining is obtained is 1.6.By the Ludox of gained with 80 DEG C of vacuum The Silica hydrogel that drying machine is dried to obtain makes it dry 3 hours and be made titanium dioxide after crushing in mortar at 180 DEG C Si powder.The hydroscopicity of the SiO 2 powder when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is 0.1 matter Amount %.

The Alpha-ray discharging amount of SiO 2 powder determines device to survey using 2 π air-flow counting mode low-levels alpha rays It is fixed, as a result it is 0.002 population/cm²Hour.

[embodiment 2]

It is set in addition to 200 DEG C except by the hydro-thermal process temperature in the operation (h) of embodiment 1, the operation with embodiment 1 A ()~(i) is similarly carried out, obtain SiO₂Concentration be 30.0 mass %, pH be 3.60, average primary particle diameter be 22nm, by moving The silica particle diameter that state light scattering determining is obtained is the acidic silicasol of 45nm.Then, with the operation (i) of embodiment 1~ Operation (k) is similarly carried out, and obtains MEK dispersion Ludox.In operation (k), the amount phase of the phenyltrimethoxysila,e of addition For the surface area 1nm of the silica dioxide granule in colloidal sol²It is 3.0.The colloidal sol of gained is as follows：SiO₂Concentration is 30.5 matter Amount %, moisture are that 0.07 mass %, methyl alcohol are 0.5 mass %, the silica particle diameter that is obtained by dynamic light scattering determination is The ratio between 45nm, the silica particle diameter/average primary particle diameter obtained by dynamic light scattering determination are 2.0.The silicon of gained is molten The Silica hydrogel that 80 DEG C of vacuum driers of glue are dried to obtain further makes it dry 3 small after crushing in mortar at 180 DEG C When and be made SiO 2 powder.SiO 2 powder when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% Hydroscopicity be 0.3 mass %.The Alpha-ray discharging amount of SiO 2 powder is 0.002 population/cm²Hour.

[embodiment 3]

In the operation (k) of embodiment 1, addition epoxycyclohexyl trimethoxy silane 15.1g substitutes phenyl trimethoxy silicon Alkane 12.1g, in addition, is carried out similarly to Example 1, obtains MEK dispersion Ludox.The epoxycyclohexyl three of addition Surface area 1nm of the methoxy silane relative to the silica dioxide granule in colloidal sol²It is equivalent to 3.0.The colloidal sol of gained is as follows： SiO₂Concentration be 30.5 mass %, moisture be 0.07 mass %, methyl alcohol be 0.5 mass %, average primary particle diameter be 45nm, by moving The silica particle diameter that the silica particle diameter that state light scattering determining is obtained is 75nm, obtained by dynamic light scattering determination/ The ratio between average primary particle diameter is 1.7.The Silica hydrogel that the Ludox of gained is dried to obtain with 80 DEG C of vacuum driers is in mortar After crushing, it is further set to dry 3 hours and be made SiO 2 powder at 180 DEG C.In 23 DEG C, relative humidity 50RH% In the environment of place 48 hours when SiO 2 powder hydroscopicity be 0.1 mass %.The Alpha-ray of SiO 2 powder is put Output is 0.002 population/cm²Hour.

[embodiment 4]

Phenyltrimethoxysila,e is substituted, relative to the surface area 1nm of silica dioxide granule contained in colloidal sol²Addition 3.0 methacryloxypropyl trimethoxy silanes, in addition, are carried out similarly to Example 1, obtain MEK point Dissipate Ludox 1000g.The colloidal sol of gained is as follows：SiO₂Concentration is 30.5 mass %, moisture is 0.07 mass %, methyl alcohol is 0.5 The silica particle diameter that quality %, average primary particle diameter be 45nm, is obtained by dynamic light scattering determination is 74nm, by dynamic optical The ratio between silica particle diameter/average primary particle diameter that scattering method is obtained is 1.6.The Ludox of gained is done with 80 DEG C of vacuum The Silica hydrogel that dry machine is dried to obtain further makes it dry 3 hours and be made titanium dioxide after crushing in mortar at 180 DEG C Si powder.The hydroscopicity of the SiO 2 powder when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is 0.1 matter Amount %.The Alpha-ray discharging amount of SiO 2 powder is 0.002 population/cm²Hour.

[embodiment 5]

Methyl alcohol dispersion Ludox (average primary particle diameter 45nm) 1000g that will be obtained by operation (a)~(j) of embodiment 1 Be dosed in 2 liters of eggplant type flask, and be stirred with magnetic stirring apparatus and meanwhile add phenyltrimethoxysila,e 4.4g it Afterwards, carry out at 60 DEG C heating for 8 hours.After being cooled to 50 DEG C, add and carry out 4 hours at HMDS 50g and then 60 DEG C Heating, so as to the methyl alcohol obtained by surface modification disperses Ludox.Then, in Rotary Evaporators, 100 DEG C of bath temperature is set, Desolventizing is carried out under the decompression of 400~20 supports, is allowed to solid and is obtained SiO 2 powder.Make the SiO 2 powder of gained Dynamic light scattering determination silica particle diameter is dispersed in MEK and utilized, is as a result 80nm.The silicon dioxide powder of gained End is as follows：The ratio between silica particle diameter/average primary particle diameter obtained by dynamic light scattering determination is 1.8,23 DEG C, it is relative The hydroscopicity of SiO 2 powder when being placed 48 hours in the environment of humidity 50RH% is less than 0.1 mass %.Silicon dioxide powder The Alpha-ray discharging amount at end is 0.002 population/cm²Hour.

[embodiment 6]

Alicyclic epoxy resin monomer (CELLOXIDE is added in the MEK dispersion sol 100g obtained by embodiment 1 2021P：Daicel Corporation) 36.7g, desolventizing is carried out under 100 DEG C of bath temperature, the decompression of 200~10 supports, obtain fat Ring type epoxy monomer disperses Ludox.The Ludox of gained is as follows：SiO₂Concentration is 45.4 mass %, MEK is less than 0.1 mass %, 23 DEG C when Type B viscosity be 1050mPas.

[embodiment 7]

Bisphenol f type epoxy resin monomer (YL-983U is added in the MEK dispersion sol 100g obtained by embodiment 1： Mitsubishi chemical Co., Ltd) 36.7g, desolventizing is carried out under 100 DEG C of bath temperature, 200~10 supports, obtain bisphenol f type epoxy resin Monomer dispersion Ludox.The Ludox of gained is as follows：SiO₂Concentration be 45.4 mass %, MEK less than 0.1 mass %, 50 DEG C When Type B viscosity be 2500mPas.

[embodiment 8]

Alicyclic epoxy resin monomer (CELLOXIDE is added in the MEK dispersion sol 100g obtained by embodiment 2 2021P：Daicel Corporation) 36.7g, desolventizing is carried out under 100 DEG C of bath temperature, the decompression of 200~10 supports, obtain fat Ring type epoxy monomer disperses Ludox.The Ludox of gained is as follows：SiO₂Concentration is 45.4 mass %, MEK is less than 0.1 mass %, 23 DEG C when Type B viscosity be 1500mPas.

[embodiment 9]

Alicyclic epoxy resin monomer is added in the MEK dispersion Ludox 100g obtained by embodiment 3 (CELLOXIDE 2021P：Daicel Corporation systems) 36.7g, carried out under 100 DEG C of bath temperature, the decompression of 200~10 supports Desolventizing, obtains alicyclic epoxy resin monomer dispersion Ludox.The alicyclic epoxy resin monomer dispersion Ludox of gained is such as Under：SiO₂Concentration be 45.0 mass %, MEK less than 0.1 mass %, 23 DEG C when Type B viscosity be 1200mPas.

[embodiment 10]

Alicyclic epoxy resin monomer is added in the MEK dispersion Ludox 100g obtained by embodiment 4 (CELLOXIDE 2021P：Daicel Corporation) 36.7g, taken off under 100 DEG C of bath temperature, the decompression of 200~10 supports Solvent, obtains alicyclic epoxy resin monomer dispersion Ludox.The alicyclic epoxy resin monomer dispersion Ludox of gained is as follows： SiO₂Concentration be 45.0 mass %, MEK less than 0.1 mass %, 23 DEG C when Type B viscosity be 1100mPas.

[embodiment 11]

The SiO 2 powder 33g that will be obtained by embodiment 5 is dosed to fibre blender (MX-X53：Panasonic Corporation systems) in, crush within 5 minutes.By alicyclic epoxy resin monomer (CELLOXIDE 2021P：Daicel Corporation systems) 70g is dosed in the cylindrical shape flask of 300ml, 80 DEG C is heated to, while being stirred with magnetic stirring apparatus Mix, while the SiO 2 powder 32g that has crushed of addition, stirring 1 hour and to obtain alicyclic epoxy resin monomer dispersion silicon molten Glue.The colloidal sol of gained is as follows：SiO₂Concentration be 30.0 mass %, 23 DEG C when Type B viscosity be 1200mPas.

[comparative example 1]

Operation (a), operation (d), operation (e), operation (f), the operation (i) of embodiment 1 are carried out in the following order, are obtained Acidic silicasol.The acidic silicasol of gained is as follows：SiO₂Concentration is that 30 mass %, pH are that 2.9, average primary particle diameter is 12nm, the silica particle diameter obtained by dynamic light scattering determination are 22nm.Acidic sol 1200g obtained by use, with reality Operation (j), the operation (k) for applying example 1 are similarly carried out, and obtain MEK dispersion Ludox.The phenyl front three of addition in operation (k) Surface area 1nm of the TMOS relative to the silica dioxide granule in colloidal sol²It is 3.3.The colloidal sol of gained is as follows：SiO₂Concentration For 30.5 mass %, moisture be 0.03 mass %, methyl alcohol be 0.5 mass %, average primary particle diameter be 12nm, by dynamic light scattering Method determines silica particle diameter that the silica particle diameter that obtains obtains for 23nm, by dynamic light scattering determination/average once The ratio between particle diameter is 1.9.After the Silica hydrogel that the Ludox of gained is dried to obtain with 80 DEG C of vacuum driers is crushed in the mortar, It is further set to dry 3 hours and be made SiO 2 powder at 180 DEG C.In the environment of 23 DEG C, relative humidity 50RH% The hydroscopicity of SiO 2 powder when placing 48 hours is 1.7 mass %.The Alpha-ray discharging amount of SiO 2 powder is 0.027 population/cm²Hour.

[comparative example 2]

In addition to not carrying out operation (b) and operation (c) in operation (a)~(i) of embodiment 1, similarly to Example 1 Carry out and obtain acidic silicasol.The acidic silicasol of gained is as follows：SiO₂Concentration be 30 mass %, pH be 2.9, it is average once The silica particle diameter that particle diameter is 40nm, obtained by dynamic light scattering determination is 80nm.Acidic silicasol obtained by use 1200g, is carried out in the same manner as the operation (j), operation (k) with embodiment 1, obtains MEK dispersion Ludox.Addition in operation (k) Surface area 1nm of the phenyltrimethoxysila,e relative to the silica dioxide granule in colloidal sol²It is 3.0.The colloidal sol of gained is such as Under：SiO₂Concentration is 30.5 mass %, moisture is 0.04 mass %, methyl alcohol is 0.5 mass %, average primary particle diameter is 40nm, The titanium dioxide silicon grain that the silica particle diameter obtained by dynamic light scattering determination is 80nm, is obtained by dynamic light scattering determination The ratio between footpath/average primary particle diameter is 2.0.The Silica hydrogel that the Ludox of gained is dried to obtain with 80 DEG C of vacuum driers is in mortar After middle crushing, it is further set to dry 3 hours and be made SiO 2 powder at 180 DEG C.In 23 DEG C, relative humidity The hydroscopicity of SiO 2 powder when being placed 48 hours in the environment of 50RH% is 0.1 mass %.The α of SiO 2 powder is penetrated The discharging amount of line is 0.025 population/cm²Hour.

[comparative example 3]

In addition to not carrying out operation (g) and operation (h) in operation (a)~(k) of embodiment 1, similarly to Example 1 Carry out, obtain MEK dispersion Ludox.The phenyltrimethoxysila,e of addition is relative to the titanium dioxide in colloidal sol in operation (k) The surface area 1nm of silicon grain²It is 3.0.The colloidal sol of gained is as follows：SiO₂Concentration is 30.5 mass %, moisture is 0.1 mass %, Methyl alcohol is that 0.5 mass %, average primary particle diameter are that 13nm, the silica particle diameter that is obtained by dynamic light scattering determination are The ratio between 28nm, the silica particle diameter/average primary particle diameter obtained by dynamic light scattering determination are 2.2.The silicon of gained is molten The Silica hydrogel that 80 DEG C of vacuum driers of glue are dried to obtain further makes it dry 3 small after crushing in mortar at 180 DEG C When and be made SiO 2 powder.SiO 2 powder when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% Hydroscopicity be 1.7 mass %.The Alpha-ray discharging amount of SiO 2 powder is 0.002 population/cm²Hour.

[comparative example 4]

In operation (a)~(k) of embodiment 1, the hydro-thermal process temperature in operation (h) is set to 180 DEG C, in addition, Carry out similarly to Example 1, obtain MEK dispersion Ludox.The phenyltrimethoxysila,e of addition is relative in operation (k) The surface area 1nm of the silica dioxide granule in colloidal sol²It is 3.0.The colloidal sol of gained is as follows：SiO₂Concentration be 30.5 mass %, Moisture be 0.1 mass %, methyl alcohol be 0.5 mass %, average primary particle diameter be 18nm, obtained by dynamic light scattering determination two Silica particle diameter is that the ratio between 35nm, the silica particle diameter/average primary particle diameter obtained by dynamic light scattering determination are 1.9. After the Silica hydrogel that the Ludox of gained is dried to obtain with 80 DEG C of vacuum driers is crushed in the mortar, further at 180 DEG C Under make its dry 3 hours and be made SiO 2 powder.When being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% The hydroscopicity of SiO 2 powder is 0.9 mass %.The Alpha-ray discharging amount of SiO 2 powder be 0.002 population/ cm²Hour.

[comparative example 5]

Commercially available water dispersible silicone colloidal sol that preparation manufactures alkoxide as raw material (Quartron (registration mark) PL-3L, SiO₂Concentration is that 19 mass %, average primary particle diameter are that 39nm, the silica particle diameter that is obtained by dynamic light scattering determination are 62nm：Fukawa Chemical Industries Co., Ltd.'s system).Water dispersible silicone colloidal sol 1000g is dosed in 2 liters of removable flask, is added Plus after methyl alcohol 200g, Tri-n-Propylamine 1.0g is added, then while being put while carrying out solvent to methanol gas are supplied in Ludox Change, obtain the methanol sol that silica concentration is 20 mass %, moisture is 1.2 mass %.Then, phenyl trimethoxy is added Silane 13.0g, is kept for 3 hours at 60 DEG C.The phenyltrimethoxysila,e of addition is relative to the silica dioxide granule in the colloidal sol Surface area 1nm²It is equivalent to 3.0.And then replaced as the methyl alcohol of decentralized medium with MEK, obtain MEK dispersed silicon Colloidal sol.The colloidal sol of gained is as follows：SiO₂Concentration is 30.5 mass %, moisture is 0.1 mass %, methyl alcohol is 0.3 mass %, average The silica particle diameter that primary particle size is 39nm, obtained by dynamic light scattering determination is 70nm, by dynamic light scattering determination The ratio between silica particle diameter/average primary particle diameter for obtaining is 1.8.The Ludox of gained is dry with 80 DEG C of vacuum driers To Silica hydrogel crush in the mortar after, it is dried 3 hours and is made SiO 2 powder at 180 DEG C. 23 DEG C, the hydroscopicity of SiO 2 powder when placing 48 hours in the environment of relative humidity 50RH% be 6.2 mass %.Dioxy The Alpha-ray discharging amount of SiClx powder is less than 0.001 population/cm²Hour.

[comparative example 6]

Added the hydrogen of the special grade chemical of commercially available product in the commercially available water dispersible silicone colloidal sol 2000g that comparative example 5 is used Sodium oxide molybdena (Kanto Kagaku K. K.'s system) is dissolved in the mass %12.6g of NaOH 10 obtained from pure water, obtains alkaline moisture Dissipate Ludox 2013g (SiO₂Concentration is 19 mass %, SiO₂/Na₂Mol ratio is 400, pH for 8.99).To 3 liters of internal volume not Aforementioned base water dispersible silicone colloidal sol 2013g is put into rust steel autoclave reactor, 30 minutes 2 hours hydro-thermals are carried out at 200 DEG C Treatment.The Ludox of gained is as follows：PH is two that 9.30, average primary particle diameter is 40nm, is obtained by dynamic light scattering determination Silica particle diameter is 66nm.It is evaporated under reduced pressure the water in the Ludox after the hydro-thermal process of gained using evaporator, by titanium dioxide Silicon concentration is carried out to adjust to 30.0 mass % in the same manner as operation (i)~(k) of embodiment 1, obtains MEK dispersion Ludox.The colloidal sol of gained is as follows：SiO₂Concentration is 30.0 mass %, moisture is 0.1 mass %, methyl alcohol is 0.3 mass %, puts down The silica particle diameter that equal primary particle size is 40nm, obtained by dynamic light scattering determination is 70nm, is surveyed by dynamic light scattering method Surely the ratio between silica particle diameter/average primary particle diameter for obtaining is 1.8.The Ludox of gained is dried with 80 DEG C of vacuum driers The Silica hydrogel for obtaining further makes it dry 3 hours and be made SiO 2 powder after crushing in mortar at 180 DEG C. The hydroscopicity of the SiO 2 powder when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is 4.9 mass %.Two The Alpha-ray discharging amount of silicon oxide powder is less than 0.001 population/cm²Hour.

[comparative example 7]

Prepare the fused silica powder (trade name of commercially available nano-scale：UFP-80, average primary particle diameter 34nm, Denka Company Limited. systems).SiO 2 powder 50g is dosed to fibre blender (MX-X53： Panasonic Corporation) in, crush within 5 minutes.To the pure water 200g that fed intake in 1 liter of beaker, before adding after crushing SiO 2 powder 50g is stated, 2 hours ultrasonications are carried out with supersonic wave cleaning machine (W-222, Honda Electronic's system) And obtain water dispersible silicone colloidal sol.Water dispersible silicone colloidal sol 250g obtained by use, carries out the operation (j) and operation (k) with embodiment 1 Same treatment.That is, the water dispersible silicone colloidal sol 250g of gained is dosed in 1 liter of removable flask, while stirring, while adding Plus methyl alcohol 50g and Tri-n-Propylamine 0.25g.Then, while supplying methanol gas while carrying out solvent displacement in Ludox, so that Obtain SiO₂The methyl alcohol dispersion Ludox 250g that concentration is 20 mass %, moisture is 1.2 mass %.Then, by the methyl alcohol of gained Dispersion Ludox 250g is dosed in 1 liter of eggplant type flask, while be stirred with magnetic stirring apparatus, while addition phenyl front three TMOS 4.0g, is heated to 60 DEG C and is kept for 3 hours.The phenyltrimethoxysila,e of addition is relative to the dioxy in the colloidal sol The surface area 1nm of silicon carbide particle²It is equivalent to 3.0.Then, eggplant type flask is installed in Rotary Evaporators, in bath temperature 80 DEG C, MEK is supplied while being distilled under the decompression of 500~350 supports, so as to obtain MEK dispersion Ludox.Gained Colloidal sol it is as follows：SiO₂Concentration is 15.5 mass %, moisture is 0.1 mass %, methyl alcohol is 0.3 mass %, average primary particle diameter The silica particle diameter obtained for 34nm, by dynamic light scattering determination is 210nm, obtained by dynamic light scattering determination two The ratio between silica particle diameter/average primary particle diameter is 6.2.The Ludox of gained is coagulated with the silicon that 80 DEG C of vacuum driers are dried to obtain Glue further makes it dry 3 hours and be made SiO 2 powder after crushing in mortar at 180 DEG C.23 DEG C, it is relative The hydroscopicity of SiO 2 powder when being placed 48 hours in the environment of humidity 50RH% is 0.1 mass %.SiO 2 powder Alpha-ray discharging amount be 0.03 population/cm²Hour.

[comparative example 8]

Prepare the vapor phase growth SiO 2 powder (trade name of commercially available nano-scale：Aerosil (registration mark) 130, Average primary particle diameter 21nm：Aerosil Corportion systems).SiO 2 powder 50g is dosed to fibre blender (MX-X53：Panasonic Corporation) in, crush within 5 minutes.To the pure water 200g that fed intake in 1 liter of beaker, powder is added Aforementioned silicas powder 50g after broken, is carried out surpassing for 2 hours with supersonic wave cleaning machine (W-222, Honda Electronic's system) Sonicated and obtain water dispersible silicone colloidal sol.Water dispersible silicone colloidal sol 250g obtained by use, is carried out and reality in the same manner as comparative example 7 Apply the operation (j) of example 1 and the treatment that operation (k) is same.The colloidal sol of gained is as follows：SiO₂Concentration is 15.5 mass %, moisture is 0.1 mass %, methyl alcohol are that 0.3 mass %, average primary particle diameter are 21nm, the silica that is obtained by dynamic light scattering determination Particle diameter is that the ratio between 150nm, the silica particle diameter/average primary particle diameter obtained by dynamic light scattering determination are 7.1.By gained The Silica hydrogel that is dried to obtain with 80 DEG C of vacuum driers of Ludox crush in the mortar after, further make it at 180 DEG C Dry 3 hours and be made SiO 2 powder.Titanium dioxide when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% The hydroscopicity of Si powder is less than 0.1 mass %.The Alpha-ray discharging amount of SiO 2 powder is less than 0.001 population/cm²· Hour.

[comparative example 9]

Using the MEK dispersion sol 100g obtained by comparative example 3, carry out similarly to Example 6, obtain ester ring type Epoxy monomer disperses Ludox.The Ludox of gained is as follows：SiO₂Concentration is 45.4 mass %, MEK less than 0.1 matter Amount %, 23 DEG C when Type B viscosity be 4500mPas.

[comparative example 10]

Using the MEK dispersion sol 100g obtained by comparative example 4, carry out similarly to Example 6, obtain ester ring type Epoxy monomer disperses Ludox.The Ludox of gained is as follows：SiO₂Concentration is 45.4 mass %, MEK less than 0.1 matter Amount %, 23 DEG C when Type B viscosity be 1800mPas.

[comparative example 11]

Using the MEK dispersion sol 100g obtained by comparative example 5, carry out similarly to Example 6, obtain ester ring type Epoxy monomer disperses Ludox.The Ludox of gained is as follows：SiO₂Concentration is 45.4 mass %, MEK less than 0.1 matter Amount %, 23 DEG C when Type B viscosity be 5000mPas.

[comparative example 12]

Using the MEK dispersion sol 100g obtained by comparative example 6, carry out similarly to Example 6, obtain ester ring type Epoxy monomer disperses Ludox.The Ludox of gained is as follows：SiO₂Concentration is 45.4 mass %, MEK less than 0.1 matter Amount %, 23 DEG C when Type B viscosity be 4800mPas.

[comparative example 13]

The MEK dispersion Ludox 100g and alicyclic epoxy resin monomer (CELLOXIDE that will be obtained by comparative example 7 2021P：Daicel Corporation) 35g mixing, entered under 100 DEG C of bath temperature, the decompression of 200~10 supports with Rotary Evaporators Row desolventizing, as a result viscosity significantly rises during desolventizing, mobility disappears.When mobility disappears, first and second Ketone has remained 3 mass %.

[comparative example 14]

The MEK dispersion Ludox 100g and bisphenol f type epoxy resin (YL-983U that will be obtained by comparative example 7：Mitsubishi Learn Co., Ltd.) 35g mixing, desolventizing is carried out with Rotary Evaporators, as a result viscosity significantly rises, flows in removing process Property disappear.When mobility disappears, MEK has remained 6 mass %.

[comparative example 15]

The MEK dispersion Ludox 100g and alicyclic epoxy resin monomer (CELLOXIDE that will be obtained by comparative example 8 2021P：Daicel Corporation) 35g mixing, entered under 100 DEG C of bath temperature, the decompression of 200~10 supports with Rotary Evaporators Row desolventizing, as a result viscosity significantly rises during desolventizing, mobility disappears.When mobility disappears, first and second Ketone has remained 2 mass %.

[comparative example 16]

The MEK dispersion Ludox 100g and bisphenol f type epoxy resin (YL-983U that will be obtained by comparative example 8：Mitsubishi Learn Co., Ltd.) 35g mixing, desolventizing is carried out with Rotary Evaporators, as a result viscosity significantly rises, flows in removing process Property disappear.When mobility disappears, MEK has remained 5 mass %.

(making of epoxy curing compound)

Use the alicyclic epoxy resin monomer dispersion Ludox or double described in embodiment 6~11 and comparative example 9~12 Phenol F types epoxy monomer disperses Ludox, and epoxy curing compound is made by the following method, the physical property of solidfied material is determined.

[embodiment 12]

To adding the alicyclic epoxy resin monomer dispersion Ludox that is obtained by embodiment 6 in the four-hole boiling flask of 300mL 40.5g and methylhexahydrophthalic anhydride 26.5g, stirs 40 minutes at 80 DEG C and obtains mixture.Then to the mixture It is middle to add as the 4-butyl-phosphonium O, O '-diethyl phosphorothioate (trade name of curing accelerator：HISHICOLIN (registrations Trade mark) PX-4ET：Nippon Chemical Ind's system) 222mg, stir within 10 minutes, and then carry out under reduced pressure 2 minutes Deaeration, obtains silica containing epoxy resin cure composition.The silica containing epoxy resin cure group of gained Compound does not detect residual organic solvent.The silica containing epoxy resin cure of gained is injected into mold plate (warp with composition The glass plate that is processed with releasing agent SR-2410 (Dow Corning Toray Co., Ltd. system), 2 pieces of glass plates at intervals of 3mm is thick), carry out 2 hours at 90 DEG C, the then heating of 1 hour at 150 DEG C, obtain silica containing epoxy resin and consolidate Compound.

[embodiment 13]

Alicyclic epoxy resin list is substituted using the bisphenol f type epoxy resin monomer dispersion Ludox obtained by embodiment 7 Body disperses Ludox, using methylhexahydrophthalic anhydride 22.3g, in addition, carries out similarly to Example 12, obtains Silica containing epoxy resin cured product.

[embodiment 14~16]

As Ludox, using the alicyclic epoxy resin monomer dispersion Ludox obtained by embodiment 8~10, except this with Outward, carry out similarly to Example 12, respectively obtain silica containing epoxy resin cured product.

[embodiment 17]

As Ludox, using the alicyclic epoxy resin monomer dispersion Ludox 31.8g obtained by embodiment 11, except this In addition, carry out similarly to Example 12, obtain silica containing epoxy resin cured product.

[comparative example 17~20]

As Ludox, using the alicyclic epoxy resin monomer dispersion Ludox obtained by comparative example 9~12, except this with Outward, carry out similarly to Example 12, obtain silica containing epoxy resin cured product.

[comparative example 21]

Add alicyclic epoxy resin monomer (CELLOXIDE 2021P：Daicel Corporation) 22.8g and methyl Hexahydrophthalic anhydride 27.4g, stirs 40 minutes at 80 DEG C and obtains mixture.Then added as solid in the mixture The 4-butyl-phosphonium O, O ' of change accelerator-diethyl phosphorothioate (trade name：HISHICOLIN (registration mark) PX-4ET： Nippon Chemical Ind's system) 222mg, stir within 10 minutes, and then deaeration in 2 minutes is carried out under reduced pressure, so that To epoxy resin cure composition.The epoxy resin cure of gained is injected into mold plate (through using releasing agent SR- with composition The glass plate of 2410 (Dow Corning Toray Co., Ltd.s systems) treatment, 2 pieces of glass plates it is thick at intervals of 3mm), carry out 90 2 hours at DEG C, the then heating of 1 hour at 150 DEG C, obtain the epoxy resin cured product without silica dioxide granule.

[comparative example 22]

Bisphenol f type epoxy resin monomer 22.8g and methylhexahydrophthalic anhydride 22.8g is added, 40 are stirred at 80 DEG C Minute and obtain mixture.Then to the 4-butyl-phosphonium O, O ' added in the mixture as curing accelerator-sulphur of diethyl two Substituted phosphate (trade name：HISHICOLIN (registration mark) PX-4ET：Nippon Chemical Ind's system) 222mg, carry out Stir, and then carry out deaeration in 2 minutes under reduced pressure within 10 minutes, so as to obtain epoxy resin cure composition.By the ring of gained Oxygen resin solidification composition injects mold plate (through with releasing agent SR-2410 (Dow Corning Toray Co., Ltd. system) The glass plate for the treatment of, 2 pieces of glass plates it is thick at intervals of 3mm), carry out 2 hours at 90 DEG C, then at 150 DEG C at the heating of 1 hour Reason, obtains the epoxy resin cured product without silica dioxide granule.

(evaluation of physical property of epoxy curing compound)

For the silica containing epoxy resin cured product of gained, bending strength test, light transmittance, lines are determined at 3 swollen Swollen coefficient, boil water absorption rate.

(3 measure of bending strength)

Based on JIS K-6911, it is measured using cupping machine.

The height and width of determination test piece, support test film, at its center with pressurization wedge imposed load, determination test piece Load when fractureing, calculates bending strength (σ).Set as follows：Bending strength σ：(MPa){kgf/mm²}、P：When test film fractures Load (N) { kgf }, L：Fulcrum spacing (mm), W：The width (mm) of test film, h：The height (mm) of test film.

σ=(3PL)/(2Wh²)

The modulus of elasticity in static bending (E)：(MPa){kgf/mm²It is set to F/Y：The slope of the straight line portion of load versus deflection curve (N/mm) when { kgf/mm },

E=[L³/(4Wh³)]×[F/Y]

(measure of light transmittance)

Use spectrophotometer (model UV-3600：(strain) Shimadzu Seisakusho Ltd. system) determine 200~800nm light transmittance.

(measure of linear expansion coefficient)

Linear expansion coefficient is determined as follows：It is measured based on JIS K-6911.The thickness of determination test piece, uses exactly TMA (thermodynamic analysis, Thermal Mechanical Analysis) is surveyed with load 0.05N, 1 DEG C/min of programming rate It is fixed.Linear expansion coefficient α₁With the initial length (L) of variable quantity (Δ the L1)/test film of the length of test film at 30~80 DEG C × 50=α₁To obtain.

(boiling the measure of water absorption rate)

It is measured based on JIS K-6911.In 24 hours air are carried out to test film in keeping 50 DEG C of thermostat Dried process.Test film after dried process is cooled to 20 DEG C, gravimetry in drier.Distilled in 100 DEG C of boilings The test film after dried process is put into water, is taken out after boil within 100 hours, cooled down 30 minutes in 20 DEG C of flowing water, Moisture is wiped, the weight after water suction is determined at once.

As follows, A is set：Boil water absorption rate (%), W₁：The weight (g) of the test film before boiling, W₂：Test film after boiling Weight (g).

A=[(W₂-W₁)/W₁]×100

Compared with the not silica containing epoxy resin cured product of comparative example 21,22, the asphalt mixtures modified by epoxy resin of embodiment 12~17 The water absorption rate that boils of fat solidfied material is reduced.On the other hand, the epoxy resin cured product of comparative example 17~20 to boil water absorption rate poor In the not silica containing epoxy resin cured product of comparative example 21.

The Alpha-ray discharging amount for making SiO 2 powder that Ludox is dried to obtain of embodiment 1~5 is 0.005 Subnumber/cm²Hour is following, extremely low, and the hydroscopicity when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is It is below 0.5 mass %, extremely low.

On the other hand, comparative example 1,3,4 makes the SiO 2 powder that Ludox is dried to obtain in 23 DEG C, relative humidity Hydroscopicity when being placed 48 hours in the environment of 50RH% is high, not agent of low hygroscopicity.In addition, the Ludox that makes of comparative example 2 is dried Although hydroscopicity of the SiO 2 powder for obtaining when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is 0.5 Below quality %, but Alpha-ray discharging amount is up to 0.025 population/cm²Hour.For comparative example 4,5, although Alpha-ray Discharging amount is low, but in the environment of 23 DEG C, relative humidity 50RH% place 48 hours when hydroscopicity for 6.2,4.9 mass %, It is at a relatively high, not agent of low hygroscopicity.

[table 1]

[table 2]

Viscosity at 50 DEG C of (*)

[table 3]

Industrial applicability

Ludox of the invention is the silica of and nano-scale of agent of low hygroscopicity minimum containing Alpha-ray discharging amount The Ludox of grain, can be suitable for semiconductor-sealing-purpose circuit board, semiconductor-encapsulating material.

Claims (25)

1. a kind of Ludox, it contains silica dioxide granule and the silica particle diameter/flat obtained by dynamic light scattering determination The ratio between equal primary particle size is less than 3.0, and the silica dioxide granule is as follows：Alpha-ray discharging amount is 0.005 population/cm²· It is hour following, and hydroscopicity when being placed 48 hours in the environment of 23 DEG C, relative humidity 50RH% is below 0.5 mass %, Surface modification is carried out by organic silane compound, the average primary particle diameter with 20~100nm.

2. Ludox according to claim 1, wherein, the organic silane compound has epoxy radicals.

3. Ludox according to claim 1, wherein, the silica dioxide granule is carried out in water with 200~350 DEG C Heat.

4. Ludox according to claim 2, wherein, the silica dioxide granule is carried out in water with 200~350 DEG C Heat.

5. the Ludox according to any one of Claims 1 to 4, wherein, the silica dioxide granule is with by alkali metal Aqueous silicate solution carries out the active silicic acid that cation exchange obtains and is manufactured as initiation material.

6. the Ludox according to any one of Claims 1 to 4, wherein, the silica dioxide granule is with via as follows The high-purity activity silicic acid that operation is obtained is manufactured as raw material, and the operation is：Carried out by alkali metal silicate aqueous solution Added in the active silicic acid that cation exchange is obtained after strong acid, further carry out cation exchange and anion exchange.

7. the Ludox according to any one of Claims 1 to 4, wherein, the silica dioxide granule is with via as follows The high-purity activity silicic acid that operation is obtained is manufactured as raw material, and the operation is：For in alkali metal silicate aqueous solution Carry out the active silicic acid that cation exchange is obtained after the salt of addition strong acid or strong acid, further carry out cation exchange and it is cloudy from Son is exchanged.

8. the Ludox according to any one of Claims 1 to 4, wherein, decentralized medium is organic solvent.

9. Ludox according to claim 5, wherein, decentralized medium is organic solvent.

10. Ludox according to claim 6, wherein, decentralized medium is organic solvent.

11. Ludox according to claim 7, wherein, decentralized medium is organic solvent.

12. Ludox according to any one of Claims 1 to 4, wherein, decentralized medium is resin monomer.

13. Ludox according to claim 5, wherein, decentralized medium is resin monomer.

14. Ludox according to claim 6, wherein, decentralized medium is resin monomer.

15. Ludox according to claim 7, wherein, decentralized medium is resin monomer.

16. Ludox according to claim 12, wherein, the resin monomer is epoxy monomer.

A kind of 17. SiO 2 powders, it is from the Ludox any one of Claims 1 to 4,9~10,13~16 Obtained from removing decentralized medium.

A kind of 18. silica containing composition epoxy resins, it contains：It is any in Claims 1 to 4,9~10,13~16 Ludox and epoxy monomer and epoxy hardener described in.

A kind of 19. silica containing composition epoxy resins, it contains：SiO 2 powder described in claim 17, with And epoxy monomer and epoxy hardener.

A kind of 20. silica containing composition epoxy resins, it is from the silica containing epoxy described in claim 18 The organic solvent and the epoxy hardener in the case where decentralized medium is organic solvent are eliminated in resin combination In optionally obtained from the organic solvent that includes.

A kind of 21. silica containing composition epoxy resins, it is from the silica containing epoxy described in claim 19 Obtained from eliminating the organic solvent optionally included in the epoxy hardener in resin combination.

22. silica containing composition epoxy resins according to claim 18, wherein, silica containing ratio is 10 ~90 mass %.

23. silica containing composition epoxy resins according to claim 19, wherein, silica containing ratio is 10 ~90 mass %.

A kind of 24. silica containing epoxy resin cured products, it is to make the silica containing epoxy described in claim 18 Obtained from resin composition.

A kind of 25. silica containing epoxy resin cured products, it is to make the silica containing epoxy described in claim 19 Obtained from resin composition.